New isoindolinone pigments and process for their manufacture

ABSTRACT

Isoindolinones of the formula   WHEREIN Hal denotes a chlorine or bromine atom, X denotes a direct bond or a carbocyclic or heterocyclic aromatic radical, Y denotes an oxygen or sulphur atom, R3 and R4 denote hydrogen lower alkyl or aryl radicals and R denotes a hydrogen atom or a lower alkyl, lower cycloalkyl, aralkyl or aryl group, Z denotes a hydrogen atom, n denotes the number 0 to 3, m denotes the number 1 to 4, p denotes the number 0 to 2 and q and r denote the numbers 0 or 1, with the sum of n+m+p being at most 4 are valuable pigments for solering plastics and lacquers in yellow to orange shades of outstanding fastness properties.

United States Patent 11 1 von der Crone et a1.

[ 1 Feb. 18, 1975 NEW ISOINDOLINONE PIGMENTS AND PROCESS FOR THEIR MANUFACTURE [75] inventors: Jost von der Crone, Riehen; Ernst Model, Basle; Andre Pugin, Riehen, all of Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Jan.,15, 1978 21 Appl. No.: 323,685

[30] Foreign Application Priority Data Jan, 17, 1972 Switzerland 618/72 [52] U.S. Cl. 260/325 PH, 260/240 G, 260/165,

260/308 B, 260/305 [51] Int. Cl C07d 27/50 [58] Field of Search 260/325, 165, 240, 308 B [56] References Cited UNITED STATES PATENTS 3,758,497 9/1973 Pugin et al 260/325 Primary Examiner-Joseph A. Narcavage Attorney, Agent, or Firm-Vincent J. Cavalieri [57] ABSTRACT lsoindolinones of the formula wherein Hal denotes a chlorine or bromine atom, X denotes a direct bond or a carbocyclic or heterocyclic aromatic radical, Y denotes an oxygen or sulphur atom, R and R denote hydrogen lower alkyl or aryl radicals and R denotes a hydrogen atom or a lower alkyl, lower cycloalkyl, aralkyl or aryl group, Z denotes I 10 Claims, No Drawings NEW ISOINDOLINONE PIGMENTS AND PROCESS or FOR THEIR MANUFACTURE It has been found that new valuable isoindolinone pigments of the formula R tr i I (Hal) e\ /c (Hal) 1m K (m P H a P wherein Hal denotes a chlorine or bromine atom, X de- N-*-X---N notes a direct bond or a carbocyclic or heterocyclic ar- 1 Cl ll ll Cl omatic radical, R and R denote hydrogen atoms or 1 Cl alkyl or aryl radicals, Y denotes an oxygen or sulphur atom. R denotes a hydrogen atom or an alkyl, cycloal- NH HN kyl or aryl group which is optionally substituted, for example by alkoxy, aryloxy, cycloalkyl, aryl or heterocy- C c clic radicals, Z denotes a hydorgen atom, n denotes the Cl 7 u Cl number 0 to 3 m denotes the number 1 to 4, ,p denots 0 0 IV the number 0 to 2 and r and :1 denote O or 1, with the sum of the n+m+p+ being at most 4, are obtained if a diamine of the f l wherein Y denotes a chlorine atom or the OR group,

0 and R and X have the indicated meaning, and especially of the formula H N(-N=c-)x+e=1-n;mi

01 u n (:1 is condensed in the molar ratio of 1:2 with an isoindolicl C C 01 none of the formula NH an (H211) V 40 R 0 C C OR NH H 01 1| u 01 Z C i ll wherein X has the indicated meaning and R denotes a 0 lower alkoxy group. wherein V denotes a group of the formula isglndolinonci his i as Starling substances contain, in the 2-position, an imino or thlo grup, 2 halogen atoms, 2 tertiary amino groups, for example piperi- Y y dino or morpholino groups, or especially 2 lower alk- 2 or u oxy groups, preferably methoxy groups.

/ The isoindolinones preferably correspond to the formula wherein X denotes an imino or thio group and Y denotes a halogen atom, a lower alkoxy group or a secon- O dary amino group. l l l 0R The dyestuffs according to the invention preferably C Cl correspond to the formulae Cl C e1 Y Y M m1 1 ll ll 1 a Cl C C Cl R0 0] Ii 0 NH HN 0 Cl ll VI 0 VII R0 0 C OR 01 ll 4 I ll Cl 0 i 0 III and especially to the formula with R and Y invthe indicated formulae having the indicated meaning and R and R denoting lower alkoxy groups. I

The 3,3-dialkoxy-isoindolinones are obtained according to a known process by reaction of a ocyanobenzoic acid alkyl ester of the formula (Hal) n on Zp CO O-Alkyl with an alkali alcoholate solution in a lower alcohol. As a rule it is not necessary to isolate the isoindolinone thus obtained which can, in most cases, be employed directly for the reaction with the diamine.

The 3-imino-isoindolinones are obtained according to a known process by reaction of an o-cyano-benzoic acid alkyl ester of the formula IX with ammonia.

The o-cyanobenzoic acid alkyl esters are in turn obtained in accordance with the process laid down in Patent application Ser.-No. 323,686, filed Jan. 15, 1973, by reaction of the ammonium salt of a tetrahalogenoor dihalogeno-o-cyanobenzoic acid with alkali alcoholates. alkali phenolates or alkali mercaptides and es terifciation of the reaction product with a dialkyl sulphate. U g I In the diamines of the formula la which also serve as starting substances X denotes, in the simplest'case, a direct bond. X can als represent a carbocyclic or heterocyclic aromatic radical, especially a divalent aromatic radical possessing at most two benzene nuclei.

Where a bicyclic divalent aromatic radical is concerned, the two benzene radicals can be bonded to one another by a direct bond or a bridge. Possible bridges are, for example, sulphur or oxygen atoms, imino groups and the atomic groupings of the formulae -N- HCO--, NH-CO--NH--, CH=CH-and N=N.

As examples of bicyclic diamines of which the benzene radicals are bonded directly to another there may be mentioned the diaminodiphenyls, especially those of formula I bromobenzene,

i XII wherein X V V and Z denote hydrogen or halogen atoms, alkyl or alkoxy groups containing 1 to 4 carbon atoms and X denotes a sulphur atom or a group of the formulae NHCO, NH-CO-NH, -CH=CH- or N=N.

Diaminopyrenes, diaminofluorenes, diaminochrysenes, diaminonaphthalenes, diaminopyrenes or diaminofluoranthenes may be mentioned as further examples of'polycyclic diamines.

Finally there may also be mentioned heterocyclic diamines such as diaminopyridines, diaminophenylene oxides, diaminodiphenylene sulphones, diaminocarbazoles, diaminobenzimidazoles, diamino-bisimidazoles, diamino-di-benzimidazolyls or diaminobenzthiazoles. 1

Finally it is also possible to use, as diamines, dihydra- -zones of dialdehydes or diketones of hydraz'ones of aminoaldehydes or aminoketones.

The phenylenediamines are of particular interest, especially those of the formula wherein X, has the indicated meaning and Z denotes a halogen atom, an alkyl or alkoxy group containing l to 4 carbon atoms or a phcnylazo group.

The following diamincs may be mentioned as examples: hydrazine, l,4-diaminobcnzcne, 1,3- diaminobenzene, l,3-diamino-4-methylbenzene, l,3-diamino-4-methoxybenzene, 1 l,3-diamino-2- methylbenzene, l,3-diamino-2,5-dichlorobenzene, 1,4- diamino-Zchlorobenzene, l,4-diamino2- 1,4-diamino-2,5-dichlorobenzene, l,4-diamino-2-methylbenzene, l,4-diamino-2,5- dimethylbenzene, l,4-diamino-2-methoxybenzene, 1,- 4-diamino-2,5-dimethoxybenzene, 1,4-diamino-2- chloro-5-methylbenzene, 1,4-diamino-2-chloro-5- methoxybenzene, 1,4-diamino-2-chloro- Sethoxybenzene, 4,4-diam'ino-diphenyl, 4,4 diamino-3,3"- dichlorodiphenyl, 4,4-diamino-3,3-dimethyldiphenyl, 4,4'-diamino-3,3-dimethoxydiphenyl, 4,4-diamino- 3,3'-diethoxydiphenyl, 2,2-diamino-diphenyl, 4,4- diamino-dephenylsulphide, 4,4-diaminobenzoylaniline, 4,4-diamino-2-ethoxy-benzoylaniline, 3,3-diamino-2,2-dimethoxy-benzoylaniline, 4,4- diamino-diphenylurea, 4.4-diamino- 3.3'-dimethoxy-diphcnylurea. 4.4'-dinminostilbcnc. 4.4'-diaminoazobenzcne, 2-mcthyl-4.4'- diaminoa-zobenzene, 2-mcthoxy-4, 4- diaminoazobenzene, 2,5-dimethyl-4,4'-

4-chloro-3,4'-

l,4-diamino-2,5-diethoxybenzene,

diaminoazobenzene, 2-chloro-4,3 diaminoazobenzene, 2-methyl-4,3 diaminoazobenzene, 2-methoxy-4,3 diaminoazobenzene, 2,4-diaminoazobenzene, 5-

methoxy-2,4-diaminoazobenzene, 2,4-diamino-3, 5'- dimethyl-4-acetylaminoazobenzene, 2,4-diamino-5- methoxy-3,5-dichloro-4-acetylaminoazobenzene, 4,- 4-diamino-phenyll -azo-naphthalene-l 4,4- diaminobenzophenone, 4,4'-diami nodiphenyl ether, 4,4-diaminodiphenylmethane, 2-,2'-diaminodibenzyl, 1,4-diaminonaphthalene, l,5-diaminonaphthalene, 2,7-diaminofluorene, 4,l1-diaminofluoranthene, 3,8- diaminopyrene, 2,8-diaminochrysene, 2,6- diaminopyridine, 2,6-diaminocarbazole, 3,6-diaminodiphenylene oxide, 2,7-diaminodiphenylene oxide, 2,6- diaminodiphenylene oxide, 2,7-diaminodiphenylene sulphone, 2,6-diaminobenzthiazole, 2-(4- aminophenyl)-6-amino-benzthiazole, terephthalaldehyde-dihydrazone, 4,4-diphenyldialdehydedihydrazone, 2,5-thiophenedialdehyde-dihydrazone, l,4-diacetylbenzene-dihydrazone, 4- aminobenzaldehyde-hydrazone, 4- aminoacetophenone-hydrazone, 4-aminobenzophenone-hydrazone, 4,-amino-4'methylbenzophenone hydrazone, glyoxal-dihydrazone and diacetyldihydrazone.

The condenstation in part already takes place in the cold, if necessary on warming the intimately mixed components, and particularly advantageously in the presence of inert organic solvents, that is to say solvents which do not participate in the reaction.

If starting from 3-imino-, 3-thioor 3,3-bis-tert. -amino-isoindolin-l-ones or from alkali metal salts of the 3,3'-dialkoxy-isoindolin-l-ones organic solvents which are miscible with water are advantageously used, for example lower aliphatic alcohols, such as lower alkanols, for example methanol, isopropanol or butanol, lower cyclic ethers, such as dioxane, ethylene glycol monomethyl ether and lower aliphatic ketones, such as acetone, Here, the condensation already takes place at relatively low temperatures. The reaction is advantageously carried out in the presence of agents which bind bases; as examples of such agents there may be mentioned lower fatty acids which can then simultaneously serve as solvents, especially acetic acid.

When using 3,3-dihalogeno-isoindolin-l-ones organic solvents which are free of hydroxyl groups are preferred, such as hydrocarbons, for example aromatic hydrocarbons, such as benzene, toluene, xylene, tetrahydronaphthalene or diphenyl, or cycloaliphatic hydrocarbons, for example cyclohexane, but also halogenated hydrocarbons, such as aliphatic halogenated hydrocarbons, for example carbon tetrachloride or tetrachloroethylene, or aromatic halogenated hydrocarbons, such as chlorobenzene or dichlorobenzenes and trichlorobenzenes, also aromatic nitro-hydrocarbons, such as nitrobenzene, ethers, namely aliphatic ethers, such as dibutyl ether, aromatic ethers, such as diphenyl ether, or cyclic ethers, such as dioxane, and also ke tones, such as acetone, or esters, especially esters of lower fatty acids with lower alkanols, such as ethyl acetate, in the presence of acid-binding agents The new pigment precipitates from the reaction medium immediately after it has formed. For certain purposes it can be used directly as the crude pigment; however it is advantageous to condition it, according to methods which are in themselves known, before it is used, for example by extraction with organic solvents or by grinding with grinding auxiliaries which can subsequently be removed again, for example salts or especially hexachloroethane, or by alkaline reprecipitation. In this way the purity, tinctorial strength and transparency can be improved yet further.

The new dyestuffs are valuable pigments which in a finely divided form can be used for pigmenting high molecular organic material, for example cellulose ethers and cellulose esters, such as ethylcellulose, acetyl-cellulose or nitrocellulose, polyamides, polyurethanes or polyesters, natural resins or synthetic resins. for example aminoplasts, especially thermoplastic and curable acrylic resins, urea-formaldehyde and melamine-formaldehyde resins and also alkyd resins, phenoplasts, polycarbonates, polyolefines, such as polysty rene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, rubber, casein, silicone and silicone resins, individually or as mixtures. Here it does not matter whether the high molecular compounds mentioned are in the form of plastic masses or melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the end use it proves advantageous to use the new pigments as toners or in the form of preparations. The new pigments are distinguished by high fastness, especially by outstanding fastness to light, migration and weathering.

EXAMPLE 1 7.9 g of 3-imino-4,5,7-trichoro-6methylmercaptoisoindolin-l-one and 1.35 g. of p-phenylenediamine in 100 ml of glacial acetic acid are heated to the reflux temperature for /2hour. The pigment formed is filtered off hot and washed with methanol and water. After drying, 7.5 g of a yellowish-tinged orange pigment, which can be employed for pigmenting lacquers and plastics, are obtained. The fastness to migration and to light is outstanding.

EXAMPLE 2 If instead of the methylmercapto compound 10.2 g of 3-imino-4,5,7-trichloro-6-phen0xy-isoindolin-l-one are used, a strongly coloured yellow pigment is obtained, which also shows very good fastness to migration and to light.

.EXAMPLE 3 EXAMPLE 4 15.5 g of 3,4,6-trichloro-S-methoxy-o-cyanobenzoic acid methyl ester are stirred with 70 ml of methanol and 8.8 g ofa 30.6 percent strength solution of sodium methylate in methanol for /2 hour. The sodium salt of 3,3,6-trimethoxy-4,5,7-trichloroisoindolin-l-one ,is thereby produced. 2,7 g of p-phenylenediamine are now added and the mixture is subsequently stirred for 2 hours at room temperature and is then diluted with 100 ml of o-dichlorobenzene. The reaction mixture is heated to 100C whilst distilling off the methanol-and stirring well. After adding a further 100 ml of odichlorobenzene and 10 ml of glacial acetic acid the temperature is raised to 140150C and maintained for 2 hours. The insoluble dyestuff is filtered off at 100C and washed with alcohol, acetone and water. After drying, 15.6 g of a reddish-tinged yellow pigment are obtained, which can be directly incorporated, in this form, into plastics and lacquers. Dyeings which are distinguished by high fastness properties such as, for example, outstanding fastness to migration in PVC or fastness to weathering in lacquers, are obtained.

The tinctorial strength and purity can be improved lffin this example, the 2.7 g of p-phenylene-diamine are replaced by equimolar amounts of the diamines listed in column A in Table l, pigments which display high fastness properties are again obtained. Column B describes the colour in lacquers.

Table I Example A v B y No. Diamines Colour 5 Q1115 I yellow E 3 redbrown OCH ctr 7 NHQ Q Z vyellow- (2H orange 8 greenish tinged yellow greenish 9 I "tinged H 11 EH I yellow 10 1 g yel'low Table I (Continuation) Example a 0 A Diaaines,

Colour tinged yellow green 15hgreenishyellow tinged yellow brown erange jr el low Table I (Continuation) Example A B No Diamines Colour N 2 greenish- 38 NH -N tinged 2 iv Cl. yellow CH CH I 39 NH --N T 2 yellow 2 40 N11 n i Z I yellQW c 0 41 NH -2 -N K 11 t 2 N C1 ow on o 42 NH 3 i 2 ellow 2 N 0011 y on o r i 3 NH 43 NH E 1 f 2 reddish?- tinged v 2 CH yellow 11 m v i N greenish- +4 l 2 g d v N H yellow OCH EXAMPLES 45 to 73 if in Example 4, instead of the 15.5 g of 3,4,6-

trichloro-5-mcthoxy-o-cyanobenzoic acid'methyl ester.

cquimolar amounts of the o-cyanobenzoic acid methyl cstcrs listed in column A olTahlc ll arc used and exactly the same procedure is followed. sparingly soluble.

dycstull's arc again produced. They are suitable for pigmcnllng plastics and lacquers and show, in PVC. the

.. Table II Example A B Colour I c1 r c1 CN yellow H 00 COOCH. M 5 2 Cl 5 4 c1 CN 46 v yellow- H c 0 0000 9 01 L5 47 yellow CH. OH (1 0 00001-1 5 4 2 Cl 5 8 yellow c n s coocn c1 :1 (m 50 reddishtinged c1-@0x (10001-1 yellow l c1 (:1 cu

51 'zgddisl w 11 ed .c11 -0 cl (200cm iiyelfow Example A B Colour Cl Cl CN reddish- 52 c tinged v c1 000C113 yellow 01 CN v v Q COOCH} yellow Cl 1 m 01 OH reddish- 54 Y tinged l yellow 0 N--0 coocm 2 c1 c1 on 55 yel 'low- 'cH o' 'o (300611 C1 C1 CN 56 r Q yellow Q-m. 1 coocn CF Cl c1 7 01 CN 57 v yellow coo I greenish- Cl 0N0 tinged v 58' yellow o OOOCH 01' 3 w (Continuation) Example A B No. Colour C1 CN yellow .M -0(cH);,-s c000 66 jellow '4 7 H 0 0 Cl COOCH I Br J Br CN,

67 v yellow l c 0 C000 4 c1 1 Br Y I 3 Br CH 68 I I Q I yellow I @.0 c0001; Br 7 Table III Example I A B C 69 orange Table III. Continuation) Example A B C C N32 01 CN r 7O 7 orange es 5 C000 H c1 c1 CH 71 I yel'low cu s c00c H E Q OCH 01 CH 7 2 IilH NH orange cn o Cl 000 j o0: 2 75 fi orange J C J EXAMPLE 74 EXAMPLE 76 Mixed synthesis. If in Example 4, instead of the 15.5 of 3,4,6-trichloro-5-methoxy-o-cyanobenzoic methyl ester a mixture of 7.75 g of this ester and 9.4 g of 3,4,6-trichloro-5-phenoxy-o-cyanobenzoic methyl ester is used and exactly the same procedure is followed, a yellow pigment is obtained which is suitable for pigmenting plastics and lacquers.

If in duced.

the

preceding 3,4,6-trichloro-5-phenoxy-o-cyanobenzoic acid methyl ester are replaced by 7.9 g of 3,4,5',6-tetrachloro-o- 65 cyanobenzoic acid methyl ester, a yellow pigment which displays high fastness properties is again pro EXAMPLE 75 example the acid EXAMPLE 77 0.6 g of the pigment manufactured according to Ex- 9.4 g of ample 4 is mixed with 67 g of polyvinyl chloride, 33 g of dioctyl phthalate, 2 g of dibutyl-tin dilaurate and 2 g of titanium dioxide and the mixture is milled for 15 minutes on a triple-roll mill. The colour of the yellow polyvinyl chloride films produced therewith is fast to migration, heat and light.

27 28 EXAMPLE wherein X V,, V and Z denote hydrogen, halogen. 10 g of titanium oxide and 2 g of the pigment manualkyl of 1 to 4 Carbon atoms, alkOXY of l to 4 Carbon lacturcd according to Example 4 and listed under l4 in atoms, 2 denotes Sulphur, the table are ground with 88 g of a mixture of 26.4 g 5 1 15 0- ol' coconut alkyd resin, 24.0 g of melaminealkyl OH to 4 carbon atoms alkoxy f 1 to 4 formaldehyde resin (50% solids content), 8,8 g of ethatOmS, ph nyl phenylazo S ubStltuteC i with ylcnc glycol monomethyl ether and 28.8 of xylene f methyl or acetylamlno, or a heterocyclic aromatic radi- 48 ho rs in a b ll ill cal, selected from the group consisting of T O L O K 1.

CH H

/ a gamer ll this lacquer is sprayed onto an aluminium toil, prc- Y denotes oxygen or sulphur, R and R, denote hydrodried for 30 minutes at room temperature and subsegen, lower alkyl or an aryl radical'selected from the quently stoved for 30 minutes at 120C, an orange l'acgroup consisting of chlorophenyl, or dichlorophenyl', quering which is distinguished by very good fastness to and R denotes hydrogen, lower alkyl, lower cycloalkyl, overlaequering, light and weathering is obtained. 3 benzyl or aryl selected from the group consisting of We claim; 0 phenyl, chlorophenyl, methylphenyl, dichlorophenyl. 1. An isoindolinone pigment of the formula dimethyl-phenyl, methoxyphenyl or naphthyl. Z de- R3 R -l 1 In (N= X (C=N; N (Hal) Hal) R) 1m I P l 0 P wherein Hal denotes chlorine or bromine, X denotes :1 notes hydorgen, n denotes the number O'to 3, m dedirect bond, a carbocyclic radical selected from the notes the number 1 to 4, p denotes the number 0 to 2 group consisting of naphthylene, or a group having the and q and r denote the numbers 0 or l, with the sum formula of n+m+p being at most 4.

29- 30 2. An isoindolinone pigment according to claim 1, of wherein X denotes hydrogen or halogen or alkyl conthe formula taining from 1 to 4 carbon atoms or alkoxy containing 1 to 4 carbon atoms and Z denotes alkyl containing from 1 to 4 carbon atoms, alkoxy containing 1 to 4 carbon atoms, phenylazo, phenylazo substituted by methyl or acetylamino.

6. The compound according to claim 2 of the formula ll C1. Cl 3 C .0

\ NH HN I wherein Y, denotes chlorine or the OR group and R CH O C/ OCH and X have the indicated meaning. 15 5 r il 3 3. An isoindolinonc pigment according to claim 2, of Cl 0 C1 the formula N -X N Cl ll ll C1 Cl C :C Cl

\ NH HN R o g o c 0R 2 c1 n n 01 2 wherein X has the indicated meaning and R denotes alkyl containing 1 to 4 carbon atoms.

4. An isoinclolinone pigment according to claim 2, of

the formula 8. The compound according to claim 2 of the formula N C i 01 C 1 NH c C1 0 C 1 0 1 0 A I O 3 N X N 9. The compound according to claim 2 of the formula 01 ll ll 01 .Cl C I C Cl N 00H H i NH HR Cl C\ R S C C SR NH CH O 2 01 ll ll Cl 3 0 0 Cl 0 whcrein X anmd R have the indicated meaning 10. The compound according to claim 2 of the for- 5. The isoindolinonc pigment according to claim 1 mull wherein X denotes the radical of the formula 0'1 1 Cl /C 

1. AN ISOINDOLINONE PIGMENT OF THE FORMULA
 2. An isoindolinone pigment according to claim 1, of the formula
 3. An isoindolinone pigment according to claim 2, of the formula
 4. An isoindolinone pigment according to claim 2, of the formula
 5. The isoindolinone pigment according to claim 1 wherein X denotes the radical of the formula
 6. The compound according to claim 2 of the formula
 7. The compound according to claim 2 of the formula
 8. The compound according to claim 2 of the formula
 9. The compound according to claim 2 of the formula
 10. The compound according to claim 2 of the formula 